CH4 Adsorption Research Articles

Maximizing Methane and Hydrogen Delivery Capacity by Carbon and Boron Nitride Nanoscrolls

The CH4 and H2 delivery capacity of carbon and boron nitride (BN) nanoscrolls was investigated, with a focus on optimizing the interlayer and van der Waals spacings to meet the U.S. Department of Energy (DOE) targets. Through computational simulations, the effects of interlayer spacing on CH4 and H2 adsorption were evaluated, revealing that while delivery quantities increase with interlayer spacing, achieving DOE targets remains a challenge for CH4. Notably, BN nanoscrolls exhibited higher adsorption capacities compared to carbon nanoscrolls, especially under low-pressure conditions. Conversely, carbon nanoscrolls displayed greater release quantities than BN nanoscrolls. For H2, delivery quantities met DOE targets at larger interlayer spacings, with carbon nanoscrolls requiring a spacing greater than 0.9 nm and BN nanoscrolls greater than 1.1 nm. For CH4 delivery, temperature optimization showed significant peaks in delivery for carbon nanoscrolls at 248 K. In contrast, BN nanoscrolls did not exhibit a peak in delivery. In carbon nanoscrolls, the optimal weight and volumetric capacities for methane delivery are 0.275 g/g and 182 cm3/cm3, respectively. Meanwhile, for hydrogen, the maximum delivery achieved is 8.26 wt% and 0.044 kg/L, which surpasses the DOE’s storage target of 5.5 wt% and 0.04 kg/L. The study also highlighted the importance of structural parameter optimization, with a significant increase in weight delivery (>500%) and in volume delivery (>120%) for both gases.

Isoreticular Contraction in Dicopper Paddle-Wheel-Based Metal-Organic Frameworks to Enhance C2H2/CO2 Separation.

Achieving a balance between high selectivity and uptake is a formidable challenge for the purification of acetylene from mixtures with carbon dioxide, particularly when seeking to maximize both C2H2 adsorption capacity and C2H2/CO2 separation selectivity in crystalline porous materials. In this study, leveraging the principles of reticular chemistry, we selected two tetracarboxylate-based linkers and combined them with Cu2+ ions to synthesize two isoreticular dicopper paddle-wheel-based metal-organic frameworks (MOFs): Cu-TPTC (terphenyl-3,3',5,5'-tetracarboxylic acid , H4TPTC) and Cu-ABTC (3,3,5,5-azobenzenetetracarboxylic acid, H4ABTC). The structural and sorption analyses revealed that Cu-ABTC, despite having slightly smaller pores due to the strategic replacement of a phenyl ring with an azo group between two tetratopic ligands, maintains high porosity compared to Cu-TPTC. Furthermore, Cu-ABTC outperforms Cu-TPTC in terms of C2H2 adsorption capacity (196 cm3 g-1 at 298 K and 1 bar) and C2H2/CO2 separation selectivity (16.5~5.6). These findings were corroborated by dynamic breakthrough experiments and computational modeling. This research highlights the potential of the isoreticular contraction strategy in enhancing MOFs for sophisticated gas adsorption and separation processes.

Simulation Study on Diffusion and Local Structure of CH4, CO2, SO2, and H2O Mixtures into Double-Layers Graphene.

Graphene has been widely studied as an ideal material for the adsorption and separation. In this work, we used molecular dynamics simulations to investigate the evolution of diffusion and local structure of CH4, CO2, SO2, and H2O mixtures into double-layers graphene under seven different interlayer spacings and four different CO2 concentrations. The results showed that the adsorption of CH4 and CO2 molecules on the graphene surface weakened with increased interlayer spacing. The diffusion capacities of CH4 and CO2 in the mixed system were significantly improved by increasing the interlayer spacing. In interlayer spacings ranging from 5 to 10 nm, the diffusion capacities of each component varied significantly in the order CH4 > CO2 ≫ H2O > SO2. Compared with CH4 and CO2, the local structures of SO2 and H2O were more affected by the interlayer spacing. Larger interlayer spacings or higher CO2 concentrations were advantageous for the formation of stronger hydrogen bond structures between H2O molecules. When the CO2 concentrations were between 10% and 20% and the interlayer spacing of graphene was 8 nm, the graphene structure exhibited the best adsorption and separation effects on CH4 and other components.

A Grafting Hydrogen‐bonded Organic Framework for Benchmark Selectivity of C2H2/CO2 Separation under Ambient Conditions

AbstractReticular chemistry and pore engineering have garnered significant advancements in metal–organic frameworks and covalent organic frameworks, leveraging robust metal‐coordination and covalent bonds. However, these achievements remain elusive in hydrogen‐bonded organic frameworks, hindered by their inherent weakness in hydrogen bonding. Herein, we strategically manipulate the porosity of hydrogen‐bonded frameworks through a grafting approach, culminating in the synthesis of two isomorphic HOFs, HOF‐FJU‐99 and HOF‐FJU‐100, with distinct pore environments. Remarkably, HOF‐FJU‐100, with its microporous architecture, not only showcases exceptional stability but also achieves unparalleled separation efficiency and ultrahigh selectivity for C2H2/CO2 mixtures (50/50, v/v) under ambient conditions. Its IAST selectivity value of 201 stands as a benchmark, towering over all previously reported HOFs. The pore of HOF‐FJU‐100 boasts an electrostatic potential highly favourable for C2H2 adsorption, as evidenced by single crystal X‐ray diffraction analysis revealing multiple hydrogen bonding interactions between C2H2 molecules and the framework. In situ gas‐carrier powder X‐ray diffraction analysis underscores the adaptability of pore structure, dynamically adjusting its orientation in response to C2H2, thereby enabling a highly efficient and specific separation of C2H2/CO2 mixtures through specific adsorptive interactions.

Conceptual Examination of Pt Atom-Adorned WTe2 for Improved Adsorption and Identification of CO and C2H4 in Dissolved Gas Analysis

The online monitoring of transformer insulation is crucial for ensuring power system stability and safety. Dissolved gas analysis (DGA), employing highly sensitive gas sensors to detect dissolved gas in transformer oil, offers a promising means to assess equipment insulation performance. Based on density functional theory (DFT), platinum modification of a WTe2 monolayer was studied and the adsorption behavior of CO and C2H4 on the Pt-WTe2 monolayer was simulated. The results showed that the Pt atom could be firmly anchored to the W atoms in the WTe2 monolayer, with a binding energy of −3.12 eV. The Pt-WTe2 monolayer showed a trend toward chemical adsorption to CO and C2H4 with adsorption energies of −2.46 and −1.88 eV, respectively, highlighting a stronger ability of Pt-WTe2 to adsorb CO compared with C2H4. Analyses of the band structure (BS) and density of states (DOS) revealed altered electronic properties in the Pt-WTe2 monolayer after gas adsorption. The bandgap decreased to 1.082 eV in the CO system and 1.084 eV in the C2H4 system, indicating a stronger interaction of Pt-WTe2 with CO, corroborated by the analysis of DOS. Moreover, the observed change in work function (WF) was more significant in CO systems, suggesting the potential of Pt-WTe2 as a WF-based gas sensor for CO detection. This study unveils the gas-sensing potential of the Pt-WTe2 monolayer for transformer status evaluation, paving the way for the development of gas sensor preparation for DGA.

Theoretical Calculation of Dissolved Gas in Transformer Oil Using the Gas Sensitive Properties of Sc- and Ti-Modified ZrS2.

To guarantee the secure functioning of the complete power system and minimize the risks associated with oil-filled transformers during their operation, it is greatly important to carry out gas sensing studies of dissolved gases in transformer research. Through the utilization of first-principles density functional theory calculations, the adsorption energy, electronic characteristics, and recuperation duration of ZrS2 modified with Sc and Ti were examined. The results show that compared to those of the initial ZrS2 material, the doping of TM atoms Sc and Ti significantly improved the adsorption properties of the material, and the adsorption of CO and C2H4 showed chemisorption. The adsorption capacity for gases decrease in the following order: C2H4 > CO > H2. The calculated recovery times indicate that Sc-ZrS2 and Ti-ZrS2 were ideal carbon monoxide sensing materials under the specific conditions. The results of this work can establish a fundamental rationale for the use of ZrS2 in sensing the conditions of oil-immersed transformers.

Evaluation of APTES-Functionalized Zinc Oxide Nanoparticles for Adsorption of CH4 and CO2.

ZnO nanoparticles functionalized with APTES were obtained to evaluate their CH4 and CO2 adsorption at 298 K in a range between 0 and 10 bar. First, ZnO nanoparticles were obtained by a precipitation method and subsequently coated with (3-aminopropyl)triethoxysilane (APTES). As a preliminary study, the results were compared with previously reported naked nanoparticles in order to evaluate the influence of APTES coating on CO2 selectivity. UV-Vis, FT-IR spectroscopy, TGA, XRD, TEM/EDX, XPS and N2 adsorption at 77 K were used to characterize the evaluated material. It was observed that the amount of gas adsorbed on the surface of the nanostructure was very small in comparison with other materials traditionally used for this purpose but slightly higher than those obtained in naked nanoparticles evaluated in previous studies. The affinity of CO2 for the amines groups of the APTES ligand was also discussed.

Differential adsorption of H2S/CH4 by bituminous coal and its competitive adsorption properties

To investigate the adsorption characteristics and competitive adsorption patterns of H2S and CH4 in coal seams, we conducted a combined experimental and molecular simulation study using Ningxia Shuangma bituminous coal as the research subject. The experiments examined the adsorption of single-component H2S and CH4 gases at different temperatures and pressures, while the molecular model of bituminous coal was used to analyze the adsorption patterns of binary gas mixtures under competing conditions. Our experimental results demonstrate that both H2S and CH4 follow Langmuir’s model, with their saturated adsorption positively correlated with pressure but negatively correlated with temperature. Moreover, under identical conditions, H2S exhibits 2.43 times higher saturated adsorption than CH4. Molecular simulations reveal that temperature has a greater impact on H2S compared to CH4; both gases undergo reversible physisorption, where isosteric heat of adsorption decreases linearly with increasing amount of adsorbate molecules; interaction energy for H2S is larger in absolute value than that for CH4, indicating its stronger affinity towards coal surfaces; regarding binary component adsorption, an increase in proportion of H2S within the gas mixture leads to higher saturation adsorptions for both the mixture itself and individual H2S molecules while decreasing saturation adsorption for CH4; Coal adsorption selectivity factor for H2S/CH4 > 1. The preferential occupation of high-energy adsorption sites is more likely to be observed for H2S. The adsorption capacity and competitive adsorption capacity of H2S were greater than that of CH4.

Research on the microscopic mechanism and model applicability differences of CH4 and CO2 adsorption based on molecular dynamics

To verify the accuracy and rationality of the molecular simulation model, the microscopic mechanism of gas adsorption was analyzed and clarified from a microscopic perspective. The effect of molecular models created by direct construction and supercell expansion on the adsorption capacities of CH4 and CO2 has been analyzed. Eight coal-based molecular configurations were created to simulate the isothermal adsorption process of CH4 and CO2 using various coal-based molecular configurations. Using physical experiments, the validity of different construction methods for coal-based molecular structures was verified. The direct construction method was chosen to simulate the effect of various coal-based molecular numbers on the adsorption capacity of CH4 and CO2. The results show that the adsorption capacity of CO2 on coal is greater than that of CH4. The isothermal adsorption curves of CH4 and CO2 in coal-based molecular systems constructed using different methods reveal that the adsorption of methane on coal molecules adheres to the Langmuir monolayer adsorption theory. The adsorption sites for methane increase with the rise in free volume. The structure directly constructed and the supercell expansion directly determines the amount of methane adsorbed by each coal based molecule. The adsorption constants of CH4 and CO2 on the supercell extended structure are more volatile than those on the directly constructed structure, and the structure constructed directly for different coal based molecules is better than the supercell extended structure. The simulation using the direct construction method shows that as the number of coal-based molecules in the molecular configuration increases, The isothermal adsorption quantities of CH4 and CO2 increase linearly. The molecular configuration is not affected by the number of anthracite molecules. Molecular configuration is not affected by the number of anthracite molecules. The rationality of model construction has no obvious relationship with the number of coal based molecules.

Boosting C2H2/CO2 separation by porous organic cages through the amino-functionalization of cavities

The in-depth investigation of the structure–property relationship in porous organic cages (POCs) for real gas mixture separation is both significant and challenging. In this work, we employed microenvironment modulation strategy to systematically regulate the gas adsorption and separation performance of POCs. The introduction of amino groups into the cavity of [2 + 4] lantern-shaped POC (CPOC-108) can effectively facilitate multiple host–guest interactions in confined cavities via forming hydrogen bond interactions. The as-prepared amino-functionalized POC (CPOC-108-NH2) thus exhibits remarkably enhanced C2H2 and CO2 adsorption capacities, especially for the more polarizable C2H2 gas, as well as higher C2H2/CO2 selectivity in comparison to CPOC-108. More importantly, CPOC-108-NH2 displays significantly improved separation performance for C2H2/CO2 mixture, as evidenced by dynamic breakthrough experiments. This work provides an elegant example for a comparative study on C2H2/CO2 separation properties between amino-functionalized and unsubstituted POCs, and may shed light on fine-tuning the cavity surfaces of POCs to rationally regulate their properties.

Nano-sized MIL-101(Cr) MOF for CO2 separation: Crystal downsizing effects on adsorption and mixed matrix membranes

In this paper, nano-sized MIL-101(Cr) metal–organic framework (MOF) and the micro-sized one were synthesized. To reduce the average crystal size, a surfactant namely cetyltrimethylammonium bromide (CTAB) in its optimum amount (Cr3+:CTAB = 1:0.3) along with microwave heating (600 W, 30 min) were applied. The prepared MOFs were characterized by FESEM, EDS, PXRD, BET, FTIR, and TGA analyses. Moreover, CO2 and CH4 adsorption isotherms and kinetics were investigated at 298 K and equilibrium pressures up to 1 bar. The results revealed that the CO2/CH4 ideal adsorption selectivity was improved by 27.15 % for the downsized MOF, so-called MIL-101(Cr)/CTAB, compared to the micro-sized one. Furthermore, by incorporation of the MOFs into the Ultem® 1000 polymer, mixed matrix membranes (MMMs) were fabricated. The morphological analysis of the prepared membranes displayed proper dispersion and compatibility between the polymer and MOFs. The best separation performance was obtained for the MMM containing 20 wt% of the mesoporous MIL-101(Cr)/CTAB. For this MMM, the CO2 permeability and CO2/CH4 ideal perm-selectivity values were enhanced by ∼ 136 % and ∼ 18 %, respectively at 298 K and 4 bar, compared to the neat membrane.

Mechanochemical “Cage‐on‐MOF” Strategy for Enhancing Gas Adsorption and Separation through Aperture Matching

AbstractPost‐modification of porous materials with molecular modulators has emerged as a well‐established strategy for improving gas adsorption and separation. However, a notable challenge lies in maintaining porosity and the limited applicability of the current method. In this study, we employed the mechanochemical “Cage‐on‐MOF” strategy, utilizing porous coordination cages (PCCs) with intrinsic pores and apertures as surface modulators to improve the gas adsorption and separation properties of the parent MOFs. We demonstrated the fast and facile preparation of 28 distinct MOF@PCC composites by combining 7 MOFs with 4 PCCs with varying aperture sizes and exposed functional groups through a mechanochemical reaction in 5 mins. Only the combinations of PCCs and MOFs with closely matched aperture sizes exhibited enhanced gas adsorption and separation performance. Specifically, MOF‐808@PCC‐4 exhibited a significantly increased C2H2 uptake (+64 %) and a longer CO2/C2H2 separation retention time (+40 %). MIL‐101@PCC‐4 achieved a substantial C2H2 adsorption capacity of 6.11 mmol/g. This work not only highlights the broad applicability of the mechanochemical “Cage‐on‐MOF” strategy for the functionalization of a wide range of MOFs but also establishes potential design principles for the development of hybrid porous materials with enhanced gas adsorption and separation capabilities, along with promising applications in catalysis and intracellular delivery.

Dynamic CO2 separation performance of nano-sized CHA zeolites under multi-component gas mixtures

To identify and evaluate promising adsorbents for CO2 separation, we synthesized CHA zeolites with different cations (Na+, K+, Cs+) and crystal sizes (45 nm – CHA45 and 500 nm – CHA500), and evaluated their explored CO2 adsorption performance from CO2/N2/He and CO2/CH4/He mixtures. Grand Canonical Monte Carlo (GCMC) and molecular dynamics (MD) simulations predicted CO2, N2, and CH4 adsorption isotherms and CO2 mobilities, respectively, which were compared to experimental data. Breakthrough curve analysis was used to assess the CO2 dynamic adsorption performance. The breakthrough curve analysis shows the smaller crystal sizes (45 nm) enhance the CO2 separation due to shorter interacrystalline diffusion pathways. Notably, Cs-CHA45 removed 2.2 times more CO2 from CO2/N2/He than Cs-CHA500. K-CHA45 showed the highest CO2/N2 selectivity (108) and achieved 841mmol g−1 for CO2 capture from N2 and 721mmol g−1 for CO2 from CH4. These findings underscore the potential of CHA nanocrystals for effective CO2 separation in various applications.

AlN Nanotube Decorated with Small Tin Oxide Clusters as a Novel CH4 Sensing Material.

The success of carbon nanotubes has triggered a great deal of research interest in other one-dimensional nanomaterials with the aim of designing innovative nanostructures with attractive and distinctive attributes for applications in sensing gas molecules and toxic substances. In the present study, first-principles density functional theory calculations were exploited to assess the capability of the small tin oxide cluster (SnxOy)-decorated (6,0)aluminum nitride (AlN) nanotube for detecting methane(CH4) in terms of energetic, structural, and electronic properties. We found that SnxOy clusters were chemisorbed on the surface of the AlN nanotube due to the considerable adsorption energy and the notable charge transfer from the former to the latter. Further calculations demonstrate that the energy band gap and work function of the AlN nanotube were reduced in the presence of additives. Benefiting from the higher affinity of SnxOy toward the CH4 molecule, the Sn3O3-decorated AlN nanotube exhibited the greatest CH4 adsorption energy. The electrical conductivity increased as the energy band gap and effective mass decreased dramatically. Additionally, the type of Sn3O3-decorated AlN nanotube changed from a p-type semiconductor to an n-type one after adsorbing the CH4 molecule. Therefore, the Sn3O3-decorated AlN nanotube endows great promise as a thermopower-based, resistance-based, and Seebeck-effect-based CH4 sensing material.

Understanding the Enhanced Separation Mechanism of C2H4/C2H6 at Low Pressure by HKUST−1

The production of ethylene (C2H4) is typically accompanied by the formation of impurities like ethane (C2H6), making the separation of C2H4 and C2H6 crucial in industrial processes. Here, we investigated the S-shaped adsorption phenomenon of C2H6 on the metal–organic framework HKUST−1. The virial equation is used to fit the C2H6 and C2H4 adsorption isotherms under low coverage. The results showed that the repulsion energy between neighboring C2H6 molecules was significantly higher than that between neighboring C2H4 molecules, which was an important reason for the lower adsorption of C2H6 by HKUST−1 at low coverage. As more molecules are adsorbed, gas molecules aggregate within pores, leading to more hydrogen bonds formed between HKUST−1 and larger-sized C2H6 under high coverage conditions. This phenomenon plays a crucial role in the S-shaped adsorption behavior of HKUST−1 on C2H6. Additionally, this unique adsorption behavior allows for the efficient separation of C2H4/C2H6 mixtures at low pressures. The ideal adsorbed solution theory (IAST) selectivity of HKUST−1 for C2H4/C2H6 mixtures was 3.78 at 283 K and 1 bar, but increased significantly to 7.53 under low pressure. This unique mechanism provides a theoretical basis for the low-pressure separation of C2H4/C2H6 by HKUST−1 and establishes a solid foundation for future practical research applications.

Investigation of the Impact of Moisture in Various States on the Adsorption of CH4, N2, and CO2 by Coal.

To investigate the impact of moisture in various states on the adsorption of CH4, N2, and CO2 by coal, this study conducted isothermal adsorption experiments on dry coal for moisture and on coal with varying moisture content for CH4, N2, and CO2. The results revealed that coal moisture adsorption progresses through four stages: monolayer adsorption, multilayer adsorption, cluster formation, and condensation into free moisture filling pores. The presence of moisture in coal varies across these stages, with its impact on CH4, N2, and CO2 adsorption decreasing as moisture content increases. As the moisture content rises, the adsorption constants (a and b values) progressively decline and eventually level off. Based on differences in coal moisture states, delineated by a relative humidity of 0.50 (corresponding to a moisture content of 2.39% in experimental samples), adsorption potential theory identified low moisture content stages where the monolayer and multilayer adsorption potentials for moisture (E1 = 4.99 kJ/mol, E2 = 39.71 kJ/mol) exceeded those for CH4, N2, and CO2, suggesting competitive adsorption effects. In the high-water content stage, the mesoporous structural fractal dimension D2 of the coal samples was found to be 2.77, nearly reaching 3, as determined through liquid nitrogen adsorption experiments and fractal dimension theory. This suggests that the intricate pore structure leads to water condensation, free water formation, and pore blockage, making it the primary factor influencing the adsorption of CH4, N2, and CO2 in coals, which is inherently linked to the characteristics of coal.

Construction of a Fluorinated-Anion Pillared Metal-Organic Framework Exhibiting Dual-Pore Architecture for Simultaneous Enhancement of C2H2 Adsorption Capacity and Selectivity.

Physisorption-based separation processes represents a promising alternative to the conventional thermally driven methods, such as cryogenic separation. However, a significant challenge lies in balancing the trade-off between adsorption capacity and selectivity of adsorbents. In this study, we introduce a novel fluorinated-anion pillared metal-organic frameworks (APMOFs) featuring a dual-pore architecture, constructed using a pyridine-oxazole bifunctional ligand. The inherent low symmetry of the ligand leads to significant distortion of the fluorinated-anion pillars, resulting in a distinctive type of APMOFs characterized by dual-pore architecture. On pore structure with constrict pore width is enriched with a high density of anion fluorinated pillars, offering numerous active sites advantageous for enhancing separation selectivity. Concurrently, the other pore structure exhibits larger dimensions, facilitating increased gas molecule accommodation and thereby augmenting adsorption capacity. Gas sorption studies reveal a substantial C2H2 adsorption capacity and a high C2H2/CO2 separation selectivity. Breakthrough experiments confirm its exceptional separation performance, while theoretical investigations elucidate a sequential adsorption process within these APMOFs, underscoring the efficacy of this strategy in overcoming trade-off limits in adsorbents.

A Grafting Hydrogen-bonded Organic Framework for Benchmark Selectivity of C2H2/CO2 Separation under Ambient Conditions.

Reticular chemistry and pore engineering have garnered significant advancements in metal-organic frameworks and covalent organic frameworks, leveraging robust metal-coordination and covalent bonds. However, these achievements remain elusive in hydrogen-bonded organic frameworks, hindered by their inherent weakness in hydrogen bonding. Herein, we strategically manipulate the porosity of hydrogen-bonded frameworks through a grafting approach, culminating in the synthesis of two isomorphic HOFs, HOF-FJU-99 and HOF-FJU-100, with distinct pore environments. Remarkably, HOF-FJU-100, with its microporous architecture, not only showcases exceptional stability but also achieves unparalleled separation efficiency and ultrahigh selectivity for C2H2/CO2 mixtures (50/50, v/v) under ambient conditions. Its IAST selectivity value of 201 stands as a benchmark, towering over all previously reported HOFs. The pore of HOF-FJU-100 boasts an electrostatic potential highly favourable for C2H2 adsorption, as evidenced by single crystal X-ray diffraction analysis revealing multiple hydrogen bonding interactions between C2H2 molecules and the framework. In situ gas-carrier powder X-ray diffraction analysis underscores the adaptability of pore structure, dynamically adjusting its orientation in response to C2H2, thereby enabling a highly efficient and specific separation of C2H2/CO2 mixtures through specific adsorptive interactions.

Molecular simulation study of adsorption-diffusion of CH4, CO2 and H2O in gas-fat coal

In order to clarify the microscopic dynamics mechanism of CH4, CO2 and H2O adsorption and diffusion in coal, and to reveal the mechanism of the influence of different temperatures and pressures on the adsorption and diffusion characteristics of coal adsorbed CH4, CO2 and H2O molecules. In this paper, the macromolecular structure model of Jixi gas-fat coal was constructed, based on the Giant Canonical Monte Carlo (GCMC) and Molecular Dynamics (MD) methods. The adsorption-diffusion characteristics of CH4,CO2 and H2O single-component gases in the gas-fat coal macromolecule model at temperatures ranging from 273.15 K to 313.15 K and pressures ranging from 0.01 MPa to 15 MPa were investigated by using Material Studio software. The research results indicated that: The adsorption of three gases, CH4, CO2 and H2O, increased with the increase of equilibrium pressure, and the adsorption isotherms conformed to Langmuir type I isotherms. The amount of saturated adsorption of CH4 ranged from 11.18 to 14.37 ml/g, the saturated adsorption of CO2 ranged from 20.40 to 24.70 ml/g, and the saturated adsorption of H2O ranged from 66.61 to 84.21 ml/g. With the increase of temperature, the saturated adsorption of CH4 and CO2 both decreased, and the saturated adsorption of H2O firstly increased and then decreased, and the adsorption of H2O by low temperature and high temperature had both an inhibitory effect on the adsorption of H2O. The potential energy distributions of CH4, CO2 and H2O molecules are poisson distributed. The absolute values of the most available interaction energies are, from highest to lowest: H2O > CO2 > CH4; the activation energies for diffusion of CH4, CO2 and H2O are 12.20 kJ/mol, 3.36 kJ/mol, and 8.47 kJ/mol, respectively, and the diffusion of CO2 is the more likely to occur. The adsorption of CH4 and CO2 in coal is physical adsorption, while the adsorption process of H2O molecules is beyond the scope of physical adsorption. The absolute value of the interaction energy is H2O > CO2 > CH4 in descending order.

Monte Carlo calculations taking into account the DLP theory to study multilayer adsorption of C2H4 and CF4 on graphite

Physisorption potentials are useful for deducing the properties of adsorption systems. The adsorption behavior is a consequence of the actual potential that describes the interactions among the adsorption system. Determining the actual isotherm is a test for the correctness of a calculated adsorption potential. The physisorption interactions decrease with the film thickness, d, according to a power law as −γ/d3, where γ is the Van der Waals coefficient. In the Dzyaloshinskii, Lifshitz, and Pitaevskii (DLP) theory, γ is a function of d where γ(d) decreases with d. In the present work, the general theory of Van der Waals forces, given by DLP, is used to derive a more exact treatment of interactions among the physisorbed systems. The Monte Carlo method is used to investigate multilayer films using a lattice gas model adsorption isotherm. Critical temperatures are determined for ethylene (C2H4) and tetrafluoromethane (CF4) on graphite. These systems exhibit comparable behavior. Unlike the findings of mean field theory, our data shows that the critical temperature rises gradually as the layer number increases. On the other hand, the comparison with experimental results and measurements has shown that our calculations are more reliable and provide a better approximation in predicting film thickness. Our isotherms appear to be in better agreement with the experimental ones.